Film forming antiperspirant polymers

ABSTRACT

Novel film-forming polymers having a carbon backbone and pendant groups containing quaternised nitrogen atoms, at least one substituent on the quaternised nitrogen being hydrophobic and containing at least 8 carbon atoms, have antiperspirant properties. For use as antiperspirants, they are dissolved or suspended in a non-aqueous carrier with a small amount of water.

This application is a division of U.S. Ser. No. 08/722,591 filed Sep.27, 1996, now U.S. Pat. No. 5,869,600, which is a continuation ofPCT/GB95/00800 filed Apr. 6, 1995.

This invention relates to certain film-forming polymers and to their useas antiperspirants.

It has been known for many years to use basic aluminium chloride (ACH)as an antiperspirant material, and products containing it are commonlyavailable for example as aerosols, sticks, roll-ons, gels and creams.Whilst ACH is a very effective antiperspirant, it has some drawbacks andthere is concern generally as to the desirability of usingaluminium-containing materials for this purpose.

WO 93/24105 describes topical antiperspirant compositions consistingessentially of an effective antiperspirant amount of a non-toxicwater-insoluble occlusive film-forming polymer. Among the preferredpolymers are alkyl olefinic acid amide/olefinic acid or estercopolymers, alone or in combination with a PVP-linear alpha-olefincopolymer or other water-repellent polymer. These compositions are saidto function as antiperspirants by the formation of a water-insolubleocclusive film on the skin, which reduces under-arm perspiration. Theyare described for use with ACH or alone.

There have been many proposals in the past to apply film-formingpolymers to the skin for various purposes. The achievement of goodantiperspirancy in this way has, however, proved very difficult. Notonly is the quality of antiperspirancy difficult to find, but it is alsodifficult to overcome the important problem of providing adequatesubstantivity of the polymer towards the skin so that it remains inplace in use.

We have now devised some film-forming polymers which are novel per seand which can provide excellent substantivity when applied topically tothe skin, and additionally provide good antiperspirancy.

According to one aspect of the present invention, there is provided afilm-forming polymer comprising units of the formulae: ##STR1## whereinX is a group which can be directly quaternised by reaction with anamine, or itself comprises a quaternisable nitrogen atom;

X'-Q is quaternised X, where Q is the quaternised nitrogen geoup and X'may be non-existent;

Q has at least one quaternised nitrogen atom having at least onesubstituent thereon which is hydrophobic and contains at least 8 carbonatoms;

Y is any atom or group which cannot be directly quaternised and does notcomprise a quaternisable nitrogen atom;

R is hydrogen or alkyl (the alkyl preferably being C₁ to C₆);

m and p can each be 0 or an integer; (n+m+p) is from 20 to 2000,preferably 20 to 1000; n/(n+m+p) % is from 1% to 100% preferably 25% to95%; and wherein the polymer can contain two or more different units offormula I, formula II and/or formula III.

These polymers are useful as antiperspirants, and the invention alsoincludes an antiperspirant composition which comprises, as the main oronly active antiperspirant ingredient, a film-forming polymer of theinvention and a cosmetically acceptable non-aqueous carrier thereforwhich may be in admixture with a minor amount of water.

In the compositions of the invention, X is a group which either containsa quaternisable nitrogen atom, or which can be directly quaternised byreaction with an amine. The amine(s) can itself be in quaternised formif desired.

The compositions of the invention can contain a small amount (i.e.usually less than 5% by weight) of an aluminium antiperspirant, but ingeneral the presence of aluminium antiperspirants reduces the efficacyof the compositions and we prefer the compositions to be substantiallyfree from aluminium. The compositions can be formulated into aerosol,solid stick, roll-on, gel or cream formulations, for example.

European patent specification no. 0141269 describes certain polyvinylalcohol polymers having oxylinked pendant quaternary ammonium ortertiary amine groups, as aids in reducing moisture loss when applied toskin as conditioning lotions or ointments in cosmetic and pharmaceuticalformulations. In general, moisture loss polymers of this type functionby forming a thin film on the surface of the skin. This film reducestransepidermal loss of moisture. However, this is a different effectfrom the antiperspirancy function of ACH. An antiperspirant functions tostop or significantly reduce the aqueous discharge from sweat ducts, andthis is two or more orders of magnitude greater than transepidermalmoisture loss. Thus, film-forming polymers known for use in reducingtransepidermal loss cannot be expected simultaneously to provide anysignificant antiperspirant effect. In EP-A-0141269, the polyvinylalcohol derivatives are used in amounts from 0.5-5% by weight ofantiperspirant compositions containing conventional amounts of ACH, oneexample being 4% of the polymer in a composition containing 57% Al Zrtetrachloro-hydrex-Gly Rezol 36G (Reheis). This is quite different fromthe compositions of the present invention where amounts of ACH greaterthan about 5% tend to cause a reduction of antiperspirant efficacy.

Further, the polyvinyl alcohol polymers described in EP-A-0141269 aresoluble or dispersible in water so that they will function to reducetransepidermal loss and be compatible with conventional aqueous-basedcosmetic and personal care products. In contrast, the polymers used inthe present invention are hardly soluble or dispersible in water at all,and require an alcoholic or other non-aqueous solvent carrier. Indeed,dispersions are unstable in the presence of significant amounts ofwater.

In the polymers of the invention, it is important that the quaternarynitrogen atoms have a hydrophobic substituent of relatively large size,i.e. at least C₈. The effect of this hydrophobic substituent is to causethe polymer to change shape in the presence of any water which will bepresent during use of the polymer as an antiperspirant. It is believedthat the change of shape is such as to express the ionic groups and thissignificantly improves the substantivity towards human skin. Thepolymers of the invention thus have good substantivity and also show amarked antiperspirant effect.

A preferred substituent for the quaternary nitrogen group is asubstituted or unsubstituted hydrocarbyl group containing from 8 to 24carbon atoms. Possible substituents include, for example, halogen,amino, nitrate, hydroxyl or aryl substituents. More preferably, thehydrocarbyl group is a linear saturated group, most preferably an alkylgroup, especially of 12 to 18 carbon atoms, e.g. dodecyl or stearyl. Itis to be understood that by "antiperspirant" we mean a substance whichwhen applied to the skin as an antiperspirant reduces wetness by atleast 20%. (Federal Register, Oct. 10th 1978 (43 FR 46694) and FederalRegister, Aug. 20th 1982 (162 FR 36492).)

Conventionally, antiperspirants are usually formulated as roll-ons,sticks, aerosols, gels or creams. For the manufacture of theseformulations, it is preferred in general that the active antiperspirantbe in solution. Alternatively, a dispersion can be used provided it isrelatively stable. Since the film-forming polymers used in the presentinvention are generally not-soluble in water, they are dissolved ordispersed in a non-aqueous cosmetically acceptable carrier. The amountof film-forming polymer is generally from 1% to 20% by weight,preferably from 6% to 10% by weight. Examples of suitable carriersinclude alcohols such as ethanol, glycols such as propylene glycol,dipropylene glycol, butylene glycol, triols such as glycerol, propylenecarbonate and volatile silicones including, for example, cyclicsilicones, linear silicones and low molecular weight dimethicones. Somewater can be included provided that the composition remains as asolution or is a stable dispersion. The addition of too much water willdestabilise the dispersions. The amount of water which can be toleratedvaries from polymer to polymer and with the non-aqueous carrier, and maybe as little as 1% up to amounts of 30% or more. It will, however,always be less than the amount of non-aqueous carrier, i.e. it ispresent in minor amount relative thereto. In any particular case,routine trials will indicate the limits. It is preferred that, in thefinal formulation, some water be present.

In the case of dispersions of the invention, it is preferred that thedisperse phase be from 5 to 10 micrometres in size.

The precise choice of film-forming polymer is not critical. Among thepreferred polymers are those wherein, in the units of formula I, X' isan alkylene carbonyl oxy group (R₄ --CO--O--), a carbonyl oxyalkylenegroup (--CO--O--R₄ --), or an arylene --C₆ H₄ -- or aralkylene group--C₆ H₄ R₄ --. Preferably, X' has the formula --O.CO.CH₂ -- (the oxygenbeing attached to the --CR--group) and R is hydrogen or methyl; or X' isa carbonyloxyethylene-oxyethylene group (the carbon being attached tothe --CR--group) and R is methyl; or X' is a benzyl group (the benzyl--CH₂ being attached to Q) and the R is hydrogen. These polymers can bevariously derived from, for example, polyvinylalcohol, haloalkylpolystyrenes and polyhydroxyalkyl methacrylates. Halogens can beintroduced into hydroxy side-chains using chloroacetate, and the halogenthen quaternised.

Other preferred values for X' in the formula I units are: ##STR2##wherein each R₄ is independently an alkylene group.

Preferably, R₄ is an alkylene group of up to 6 carbon atoms, mostpreferably methylene or ethylene.

Film-forming polymers of the invention with values of X'-Q defined abovecan be made from many known polymers, including, for example,polyacrylamide, poly(haloalkylacrylate), poly(acryloyl chloride),chloromethylpolystyrene, poly(hydroxyalkyl methacrylate),polysaccharide, poly(allyl alcohol), poly(N-methylol acrylamide),poly(alkylacrylate), poly(alkylmethacrylate) and poly(glycidylmethacrylate). The side chains of these known polymers can be convertedto X'--Q side chains of the present invention in various ways, as willbe clear to those skilled in the art. For example:

(a) the Mannich reaction can be used to quaternise the amido NH₂ groupof polyacrylamide.

(b) those known polymers with halogen in the side chain can bequaternised directly by reaction with an amine.

(c) those polymers with a hydroxyl (or epoxide) group in the side chaincan be converted to the chloroacetate (or an equivalent halocarboxylate)derivative which can then be quaternised.

(d) those polymers with a carboxyl ester group can be transesterifiedwith, for example, a glycol and then treated as in (c). These proceduresare merely examples.

The polymers of the invention can also, of course, be made from knownpolymers which have at least one quaternisable nitrogen atom present ina side chain. Such known polymers include, for example, polyvinylpyridine, polyvinylimidazoline and polyvinyl imidazole. Polymers of theinvention include:

(i) those which contain formula I units of formula ##STR3## wherein R ishydrogen or an alkyl group, R₄ is a single bond or an alkylene group, R₃is hydrophobic and contains at least 8 carbon atoms, and Z⁻ is an anion.

(ii) those wherein, in the units of formula I, X'--Q is selected from##STR4## wherein R₆ is a single bond or an alkylene group. R₃ ishydrophobic and contains at least 8 carbon atoms, and Z⁻ is an anion.

Among the preferred polymers of the invention are those which compriseunits of formula II wherein X is selected from ##STR5## wherein R4 is analkylene group, and Hal is a halogen, preferably chlorine or bromine.

Preferably, R₄ contains from 1 to 6 carbon atoms and is most preferablymethylene or ethylene.

In the polymers of the invention, m and p can each independently bezero. Normally, neither m nor p will be zero. When p is not zero,preferred units of formula III include those wherein Y is selected from##STR6## wherein R₄ is an alkylene group and R₅ is an alkyl group.

Preferably, R₄ and R₅ will both contain from 1 to 6 carbon atoms, andmost preferably R₄ is methylene or ethylene.

In the quaternised polymers of the invention, the quaternary nitrogenatoms have one long chain substituent i.e. one substituent having 8 ormore, preferably 8 to 25, carbon atoms. Any hydrocarbyl group havingfrom 8 or more carbon atoms can be used. Among the preferred suchsubstituents are C₁₂ (dodecyl), C₁₆ (hexadecyl) and C₁₈ (stearyl) butother substituents may be employed, for example alkylaryl radicals. Thepreferred R₁ and R₂ substituents are hydrocarbyl, eg. alkyl groups,having from 1 to 8 carbon atoms. Methyl groups are preferred, but theymay themselves carry substituents as desired. Among the possiblesubstituents on the hydrocarbyl groups are halide, amino, nitro,hydroxyl or aryl, for example.

However, regardless of which particular values for the threesubstituents on the nitrogen are chosen, it is important that togetherthey have a hydrophobicity to promote the substantivity of the polymeras previously described. The substantivity to skin can be impaired ifthe substituents are so bulky as to cause steric hindrance to thequaternary ammonium ion. Generally, two of the groups will be smallrelative to the main hydrophobic group of at least 8 carbon atoms.

The quaternised nitrogen atoms may be attached directly to the polymericbackbone but usually instead are attached to a side chain extending fromthe backbone. In order to promote the formation and stability of thequaternary ammonium groups, the side chain will preferably include someelectron withdrawing atoms or groups. Thus, as described above, the sidechains can be formed from halocarboxylates, eg. haloacetates, bysubstituting the quaternised nitrogen at the halogen position. Otherhalogenated side chains may also be employed to make the quaternisedcompounds, for example p-chloromethylphenyl units.

The side chain can also be a tertiary aromatic amine, for example2-pyridyl or 4-pyridyl, or an aliphatic amine, for exampledialkylaminoethyl ester and the quaternary formed by using haloalkyls.

The side chain can be any alcohol or ester, the quaternary being addedeither by the use of base or Lewis acid catalysis of a ring openingaddition by a quaternised epoxy or transesterification of a trialkyloxy-ammonium halide catalysed by a transition metal catalyst.

The nature of the carbon chain backbone of the polymer is not criticalprovided that it does not contain substituents antagonistic to theintended use of the polyquat. One highly preferred material is polyvinylalcohol to which side chains can be attached via the pendant OH groups.

In the film-forming polymers of the invention, Q is preferably selectedfrom:

(a) --N⁺ R₁ R₂ R₃ Z⁻, where R₁ and R₂ are the same or different and areeach a C₁ to C₈ substituted or unsubstituted hydrocarbyl group, R₃ is aC₈ to C₂₅ substituted or unsubstituted hydrocarbyl group, and Z⁻ is ananion;

(b) ##STR7## where R₃ and each Z⁻ are independently as defined in (a)above;

(c) ##STR8## where R₃ and each Z⁻ are independently as defined in (a)above;

(d) ##STR9## where R₃ is as defined in (a) above; (e) ##STR10## where R₃and each Z⁻ are independently as defined in (a) above and q is from 2 to10.

Preferably, R₁ and R₂ are both alkyl groups. R₃ is preferably a linearsaturated hydrocarbyl group, preferably C₁₂ to C₁₈. In the aboveformulae for Q, and in all occurrences in the specification and claims,Z⁻ is preferably a halide ion, most preferably chlorine or bromine.

In the diquaternary (e) above, q is preferably 2,3 or 4.

The film-forming polymers used in the present invention can have a veryhigh antiperspirant efficacy. (Efficacy was measured using a standardforearm sweat reduction test and the standard FDA axilla sweat reductiontest (Federal Register Aug. 20th 1982 (162 FR 36492.) For example, wehave found that a concentration as low as 3% by weight in an aqueousalcohol (30% water) dispersion can be more efficacious than aconventional 20% ACH solution. The efficacy does vary among thepolymers. In general, the efficacy increases with increasing chainlength of the quaternary nitrogen substituents. Efficacy also tends toincrease with increasing water-content of the compositions.

In the quaternised polymers of the invention, it is not essential thatevery side chain (or group pendant from the main backbone chain) bequaternised. With increasing quaternisation, efficacy tends to rise butvery useful and adequate antiperspirancy can be achieved with relativelylow quaternisation. Quaternisation can be as low as 1%, but we preferfrom about 25% up to 95% or more, and more preferably at least 75%, mostespecially at least 85%.

The quaternised polymeric materials can be made in a variety of ways aspreviously described, depending on their precise constitution. Usually,however, a polymeric material with a suitably reactive side chain isreacted with a tertiary amine. For example, poly(vinylchloroacetate) canbe reacted with stearyldimethylamine to make the antiperspirant polyquatstearyldimethylamine quaternised poly(vinylchloroacetate). Thepoly(vinylchloroacetate) can be made by reacting polyvinyl alcohol withchloroacetyl chloride. Those skilled in the art will know of these typesof reactions and no further teaching in connection therewith will begiven herein.

As stated above, the antiperspirant efficacy of the polyquats isimproved by the presence of water. It is preferred, therefore, to usethem in formulations where water can be present. Accordingly, we preferto use them in roll-ons, creams, gels and stick formulations, ratherthan in aerosols.

The molecular weights of the polymers of the invention can vary widely,but we prefer to use polymers in which (m+n+p) is from 20 to 2000 units,most preferably 200 to 1000 units. In the case of a 25% degree ofsubstitution, 25% of the units in the polymer will be of formula Iabove. At very high degrees of substitution e.g. 95%, virtually all thepolymer units are those of formula I.

The polymers can contain two or more different formula I groups in thesame polymer, i.e. mixed polyquats. These polymers are usually made byusing two different amines in the quaternisation procedure. They areespecially useful in providing a bactericidal effect.

The polymers of the invention can be homopolymers or copolymers madefrom two or more monomers. It can be advantageous to use copolymers inorder to provide more closely the qualities desired in the film-formingpolymer.

For example, poly(vinylalcohol) polymers can be made softer bycopolymerising the vinyl alcohol with ethylene. In the resultingpolymers of the invention, the units derived from the ethylene areformula III units in which Y is hydrogen.

In order to make a conventional antiperspirant formulation using thefilm-forming antiperspirant polymers of this invention, a composition ofthe invention is mixed with other components of the formulation. Thevarious ways in which this is done will be clear to those skilled in theart. For example, sticks can be formed from a soap gel, a wax, or adibenzylidine sorbitol product. No detailed description thereof will begiven.

In order that the invention may be more fully understood, the followingExamples are given by way of illustration only.

EXAMPLE 1 Preparation of Chloroacetate Derivatives of Hydroxy Polymers

To the appropriate hydroxy polymer (0.1 mol) were added chloroacetylchloride (0.3 mol) and water (a few drops). The heterogeneous mixtureobtained was stirred at room temperature under anhydrous conditions for4 h. The viscous homogeneous mixture formed was diluted with ethylacetate. The polymer was precipitated into an excess of ethanol,filtered and dried under vacuum to give a light brown powder. Yield 75%.

The reaction was performed on poly(vinylalcohol) samples of molecularweight 9,000, 14,000, 22,000 and 49,000, with degrees of polymerisation(DP) of (approximately) 200, 300, 500 and 1100, respectively, anddegrees of hydrolysis of 98.4%, 88% and 80%, respectively. The degree ofhydrolysis indicates the extent of conversion of polyvinylacetate topolyvinylalcohol.)

EXAMPLE 2 Quaternisation of Poly(vinylchloroacetate) with StearylDimethylamine (SDMA)

The SDMA quaternary was prepared by reacting poly(vinylchloroacetate)with stearyl dimethylamine: ##STR11## where n=x+y.

The poly(vinylchloroacetate) was derived from 9000 molecular weightpoly(vinylalcohol) as described in Example 1. Thispoly(vinylchloroacetate) (0.1 mol) was dissolved in ethyl acetate (150ml). To this solution was added the required amount ofstearyldimethylamine. This reaction was refluxed for three hours. Thequaternised polymer precipitated out. The excess ethyl acetate wasdecanted off and the product was triturated with ethyl acetate, filteredand dried in a vacuum oven at room temperature. When an equimolar amountof SDMA was added, the substitution was about 88% by nitrogen analysis.Elemental analysis indicated 88% quaternisation.

The ratio of poly(vinylchloroacetate) to SDMA was varied as follows:1:0.5, 1:0.4, 1:0.3, 1:0.2 and 1:0.1 to provide a number of products ofvarying quaternisation. The same results were obtained whendimethylformamide was used as the solvent in place of ethyl acetate.

    ______________________________________                                                   Theory (w/w %)                                                                          Found (w/w %)                                            ______________________________________                                        Carbon       69.0        64.5                                                 Hydrogen     11.5        10.3                                                 Nitrogen     3.4         3.0                                                  ______________________________________                                    

EXAMPLE 3

Example 2 was repeated but using dodecyldimethylamine instead of stearyldimethylamine. Similar results were obtained.

EXAMPLE 4

The efficacy of various solutions of the polyquats of Examples 2 and 3was tested by routine methods and compared to conventional ACHsolutions. The results showed that the stearyl quaternary was moreefficacious than the dodecyl quaternary, and that efficacy increasedwith increasing degrees of quaternisation. In general, the efficacy wasclose to that of ACH. Substantivity to human skin was excellent. Theresults of the tests were as follows:

    ______________________________________                                        Forearm Efficacy of Polyquat Formulations                                     Formulation % w/w                                                             Polyvinyl-                Volatile                                            chloroacetate             Silicone      Efficacy                              SDMA    Polymer  Ethanol  VS 344 Water  %                                     ______________________________________                                        1:1     8        62       --     30     70.6                                          5        65       --     30     64.0                                          3.5      66.5     --     30     54.0                                          2        68       --     30     17.5                                          8        72       --     20     47.8                                          8        82       --     10     39.2                                          8        62       30     --     45.9                                  1:0.5   8        62       --     30     55.3                                  1:0.25  8        62       --     30     43.8                                  Polyvinyl-                                                                    chloroacetate                                                                 DDMA                                                                          1:1     8        62       --     30     56.6                                  1:0.25  8        62       --     30     16.8                                  The polyvinylchloroacetate is derived from                                    polyvinyl alcohol (DP 320)                                                    Standard FDA Hot Room Efficacy Test                                           Formulation % w/w                                                             Polyvinyl-                Volatile                                            chloroacetate             Silicone      Efficacy                              SDMA    Polymer  Ethanol  VS 344 Water  %                                     ______________________________________                                        1:1     8        62       --     30     28.4                                  Polyvinylchloroacetate derived from polyvinylalcohol                          (88% hydrolysed DP200)                                                        ______________________________________                                    

EXAMPLE 5 Quaternisation of the Chloroacetate Derivative ofPoly(2-hydroxyethyl methacrylate) with Stearyl Dimethylamine

The chloroacetate derivative of poly(2-hydroxyethyl methacrylate) (0.01mol) was dissolved in dimethylformamide (100 ml). To the solution wasadded stearyl dimethyldiamine (0.012 mol) and this was left stirring at60° C. for 72 h. The polymer was precipitated into an excess of ethylacetate, triturated with fresh ethyl acetate (twice) and dried undervacuum to give a pale yellow powder. Yield 60%.

Elemental analysis indicated 40% quaternisation.

    ______________________________________                                                   Theory (w/w %)                                                                          Found (w/w %)                                            ______________________________________                                        Carbon       64.8        61.2                                                 Hydrogen     10.6        9.5                                                  Nitrogen     5.4         2.2                                                  ______________________________________                                    

EXAMPLE 6 Quaternisation of Poly(4-vinylpyridine) with 1-Bromohexadecane

To a viscous solution of poly(4-vinylpyridine), molecular weight 50000,approximate DP 475, (0.02 mol) in methanol (100 ml) was added1-bromohexadecane (0.04 mol) and this was stirred under reflux for 5days. The solvent was removed under vacuum. The polymer was purified byrepeated dissolution in dichloromethane and precipitation into an excessof cold diethyl ether. The polymer was dried under vacuum to give alight-brown powder. Yield 85%. Halide analysis indicated 97%quaternisation. Analysis for bromine revealed 18.9% (19.5% expected).

EXAMPLE 7 Quaternisation of Poly(vinylbenzylchloride) with StearylDimethylamine

Poly(vinylbenzylchloride), molecular weight 55000, approximate DP 360,(2 g) and stearyl dimethylamine (3.9 g) were added to ethanol (25 ml)and heated under reflux with stirring for 24 h. The reaction mixture wasprecipitated into acetone (400 ml) and centrifuged. A white powder wasrecovered and dried under vacuum to constant weight (5 g). Elementalanalysis indicated 90% quaternisation.

    ______________________________________                                                   Theory (w/w %)                                                                          Found (w/w %)                                            ______________________________________                                        Carbon       77.4        71.8                                                 Hydrogen     11.6        10.6                                                 Chlorine     7.9         7.3                                                  Nitrogen     3.1         2.7                                                  ______________________________________                                    

EXAMPLE 8 Co-quaternisation of Poly(vinylchloroacetate) with StearylDimethylamine and 4.4'-dipyridyl N-benzyl Bromide

Firstly, monoquaternisation of 4,4'-dipyridyl with benzyl bromide waseffected as follows. Benzyl bromide (0.05 mol) was added dropwise to asolution of 4,4'-dipyridyl (0.065 mol) in dry acetone (100 ml) and themixture was refluxed for 4 h. The solid formed was filtered andcrystallised from diethyl ether:ethanol to give the pure product. Yield60%.

    ______________________________________                                                   Theory (w/w %)                                                                          Found (w/w %)                                            ______________________________________                                        Carbon       62.2        62.1                                                 Hydrogen     4.9         4.7                                                  Nitrogen     8.5         8.5                                                  ______________________________________                                    

Then, the monoquaternary of 4,4'-dipyridyl (2×10⁻⁴ mol) was added to asolution of poly(vinylchloroacetate) (0.01 mol) in dimethylformamide(100 ml) and stirred at 50° C. for 24 h. (The poly(vinylchloroacetate)was made by the method of Example 1 from poly(vinylalcohol) of molecularweight 14000, approximate DP 300.) Stearyl dimethylamine (1×10⁻² mol)was then added and heating and stirring continued for a further 48 h.The precipitate which formed was triturated with ethyl acetate (twice)and dried to give a white powder. Yield 75%.

EXAMPLE 9 Co-quaternisation of Poly(vinylchloroacetate) with StearylDimethylamine and N-octadecyl-N,N,N',N'-tetramethylethylenediamineBromide

Firstly, monoquaternisation of N,N,N',N'-tetramethylethylenediamine with1-bromooctadecane was effected as follows. 1-bromooctadecane (0.03 mol)was added dropwise to a solution of N,N,N',N'-tetramethylethylenediamine(0.04 mol) in ethanol (200 ml). The mixture was refluxed for 24 h andthe solvent removed under vacuum to give a waxy material. Yield 70%.

The monoquaternary of N,N,N',N'-tetramethylethylenediamine (2×10⁻⁴ mol)was added to a solution of poly(vinylchloroacetate) (0.01 mol) indimethylformamide (100 ml) and stirred at 50° C. for 24 h. (Thepoly(vinylchloroacetate) was made from poly(vinylalcohol) of molecularweight 14000, approximate DP 300, by the method of Example 1.) Stearyldimethylamine (1×10⁻² mol) was then added and heating and stirringcontinued for a further 48 h. The precipitate which formed wastriturated with ethyl acetate (twice) and dried to give a white powder.Yield 75%.

EXAMPLE 10 Quaternisation of Poly(vinylalcohol-co-ethylene) with SDMA

Poly(vinylalcohol-co-ethylene) was converted to the chloroacetatederivative by the process of Example 1.

The poly(vinylchloroacetate-co-ethylene) (0.04 mol, ethylene content 27mol %) was dissolved in dimethylformamide (150 ml). Stearyldimethyldiamine (0.035 mol) was added and the mixture stirred at 50° C.for 72 h. The solid precipitate which formed was triturated with freshethyl acetate (twice) and dried under vacuum to given an off-whitepowder. Yield 80%.

EXAMPLE 11 Quaternisation of Poly(styrene-co-allyl Alcohol) with StearylDimethylamine

Poly(styrene-co-allyl alcohol) molecular weight 1600, DP approximately20, was converted to the chloroacetate derivative by the process ofExample 1.

The poly(styrene-co-allyl chloroacetate) (0.04 mol. styrene content 94mol %) was dissolved in ethyl acetate (150 ml). Stearyl dimethyldiamine(3×10⁻³ mol) was added and the mixture stirred at 50° C. for 72 h. Thesolvent was removed under vacuum. The polymer was purified by repeateddissolution in dichloromethane and precipitation into an excess of colddiethyl ether. The polymer was dried under vacuum to give a pale yellowpowder. Yield 75%.

EXAMPLE 12

An example of a roll-on of the invention is:

    ______________________________________                                                         %                                                            ______________________________________                                        Polyquat (Example 2)                                                                             8.0                                                        Triclosan          0.3                                                        Water              1.0                                                        Cyclomethicone DC344                                                                             30.0                                                       Ethanol            60.7                                                       ______________________________________                                    

EXAMPLE 13

An example of a stick product of the invention is:

    ______________________________________                                                        %                                                             ______________________________________                                        Polyquat (Example 2)                                                                            8.00                                                        Ethanol           53.95                                                       Water             16.45                                                       Stearyl alcohol   14.00                                                       Castor oil        3.00                                                        Talc              2.20                                                        Silica            1.40                                                        PEG               1.00                                                        ______________________________________                                    

EXAMPLE 14

An example of an aerosol of the invention is:

    ______________________________________                                                           %                                                          ______________________________________                                        Polyvinylchloroacetate/DMA (1:1)                                                                   4                                                        Ethanol              74.5                                                     Triethyl citrate     1.5                                                      CAP 30               20                                                       ______________________________________                                    

We claim:
 1. A film-forming polymer comprising units of the formula:##STR12## wherein X is a group which can be directly quaternised byreaction with an amine, or itself comprises a quaternisable nitrogenatom;X'--Q is quaternised X, where Q is the quaternised nitrogen groupand X' may be non-existent; Q has at least one quaternised nitrogen atomhaving at least one substituent thereon which is hydrophobic andcontains at least 8 carbon atoms; Y is any atom or group which cannot bedirectly quaternised and does not itself comprise a quaternisablenitrogen atom; R is hydrogen or alkyl; m and p can independently be 0 oran integer; (n+m+p) is from 20 to 2000; n/(n+m+p) % is from 25% to 95%;and wherein the polymer may optionally contain two or more differentunits of formula I, formula II and/or formula III.
 2. The polymer ofclaim 1 wherein X'--Q is selected from ##STR13## wherein each R₄ isindependently an alkylene group of 1 to 6 carbon atoms and Q is selectedfrom ##STR14## where R₁ and R₂ are the same or different and are each ac₁ to C₈ hydrocarbyl group unsubstituted or substituted with at leastone halo, amino, nitro, hydroxyl or aryl group, R₃ is a C₈ to C₂₅hydrocarbyl group unsubstituted or substituted with at least one halo,amino nitro, hydroxyl, or aryl group, q in an integer from 2 to 10, andZ⁻ is an anion.
 3. The polymer of claim 1 wherein X'--Q is selected from##STR15## wherein R₆ is a single bond or an alkylene group of 1 to 6carbon atoms, R₃ is a C₈ to C₂₅ hydrocarbyl group unsubstituted orsubstituted with at least one halo, amino, nitro, hydroxyl or arylgroup, and Z⁻ is an anion.
 4. The polymer of claim 2 or 3 whereinX isselected from --Hal, --R₄ --Hal, --O--CO--R₄ --Hal, --CO--O--R₄ --Hal,--CO--Hal, --C₆ H₄ --R₄ --Hal, --CO--O--R₄ --O--R₄ --Hal,--CO--NH--O--CO--R₄ --Hal, --CO--O--R₄ --O--CO--R₄ --Hal; ##STR16## andY is selected from --H, --OH, --CONH₂, --CO--O--R₄ --OH, --R₄ --OH,--CO--NH--R₄ --OH, --C₆ H₅, --C₆ H₄ --R₅, --CO--O--R₅, and --CO--O--R₄--O--R₄ --OH;wherein R₄ is an alkylene group of 1 to 6 carbon atoms, R₅is an alkyl group of 1 to 6 carbon atoms and Hal is a halogen.
 5. Thepolymer of claim 4 wherein R is H or methyl, R₁ and R₂ are alkyl, R₄ ismethylene or ethylene, and Z⁻ is halide.
 6. The polymer of claim 5wherein R₃ is a linear saturated hydrocarbyl group of 12 to 18 carbonatoms.
 7. The polymer of claim 4 wherein m and p are both integers. 8.The polymer of claim 7 wherein n+m+p is from 200 to
 1000. 9. The polymerof claim 8 wherein R is H and Y is H.
 10. The polymer of claim 2 whereinX'--Q is --O--CO--CH₂ --Q and X is --O--CO--CH₂ --Cl.
 11. The polymer ofclaim 10 wherein R is H or methyl and Y is H or OH.
 12. The polymer ofclaim 11 wherein Q is --N⁺ R₁ R₂ R₃ Z⁻.
 13. The polymer of claim 12wherein R₁ and R₂ are alkyl, R₃ is a linear saturated hydrocarbyl groupof 12 to 18 carbon atoms, and Z⁻ is halide.
 14. The polymer of claim 13wherein m and p are both integers.
 15. The polymer of claim 14 wherein Ris H and Y is H.
 16. The polymer of claim 2 wherein X'--Q is --C₆ H₄--CH₂ --Q and X is --C₆ H₄ --CH₂ --Cl.
 17. The polymer of claim 16wherein R is H or methyl, Y is H or OH, and Q is --N⁺ R₁ R₂ R₃ Z⁻. 18.The polymer of claim 3 wherein X'--Q is ##STR17## wherein R is H and Z⁻is halide.
 19. A film-forming polymer comprising units of the formula:##STR18## wherein X is a group which can be directly quaternised byreaction with an amine, or itself comprises a quaternisable nitrogenatom;X'--Q is quaternised X, where Q is the quaternised nitrogen groupand X' may be non-existent; Q has at least one quaternised nitrogen atomhaving at least one substituent thereon which is hydrophobic andcontains at least 8 carbon atoms; Y is any atom or group which cannot bedirectly quaternised and does not itself comprise a quaternisablenitrogen atom; R is hydrogen or alkyl; m and p are both integers;(n+m+p) is from 20 to 2000; n/(n+m+p) % is 1% or more; and wherein thepolymer may optionally contain two or more different units of formula I,formula II and/or formula III.
 20. The polymer of claim 19 wherein X'--Qis selected from ##STR19## wherein each R₄ is independently an alkylenegroup of 1 to 6 carbon atoms and Q is selected from ##STR20## where R₁and R₂ are the same or different and are each a C₁ to C₈ hydrocarbylgroup unsubstituted or substituted with at least one halo, amino, nitro,hydroxyl or aryl group, R₃ is a C₈ to C₂₅ hydrocarbyl groupunsubstituted or substituted with at least one halo, amino, nitro,hydroxyl or aryl group, q is an integer from 2 to 10, and Z⁻ is ananion.
 21. The polymer of claim 19 wherein X'--Q is selected from##STR21## wherein R₆ is a single bond or an alkylene group of 1 to 6carbon atoms, R₃ is a C₈ to C₂₅ hydrocarbyl group unsubstituted orsubstituted with at least one halo, amino, nitro, hydroxyl or arylgroup, and Z⁻ is an anion.
 22. The polymer of claim 20 or 21 whereinX isselected from --Hal, --R₄ --Hal, --O--CO--R₄ --Hal, --CO--O--R₄ --Hal,--CO--Hal, --C₆ H₄ --R₄ --Hal, --CO--O--R₄ --O--R₄ --Hal,--CO--NH--O--CO--R₄ --Hal, --CO--O--R₄ --O--CO--R₄ --Hal; ##STR22## andY is selected from --H, --OH, --CONH₂, --CO--O--R₄ --OH, --R₄ --OH,--CO--NH--R₄ --OH, --C₆ H₅, --C₆ H₄ --R₅, --CO--O--R₅, and --CO--O--R₄--O--R₄ --OH; wherein R₄ is an alkylene group of 1 to 6 carbon atoms, R₅is an alkyl group of 1 to 6 carbon atoms and Hal is a halogen.
 23. Thepolymer of claim 22 wherein R is H or methyl, R₁ and R₂ are alkyl, R₄ ismethylene or ethylene, and Z⁻ is halide.
 24. The polymer of claim 23wherein R₃ is a linear saturated hydrocarbyl group of 12 to 18 carbonatoms.
 25. The polymer of claim 22 wherein n/(n+m+p) % is from 25% to95%.
 26. The polymer of claim 25 wherein n+m+p is from 200 to
 1000. 27.The polymer of claim 26 wherein R is H and Y is H.
 28. The polymer ofclaim 20 wherein X'--Q is --O--CO--CH₂ --Q and X is --O--CO--CH₂ --Cl.29. The polymer of claim 28 wherein R is H or methyl and Y is H or OH.30. The polymer of claim 29 wherein Q is --N⁺ R₁ R₂ R₃ Z⁻.
 31. Thepolymer of claim 30 wherein R₁ and R₂ are alkyl, R₃ is a linearsaturated hydrocarbyl group of 12 to 18 carbon atoms, and Z⁻ is halide.32. The polymer of claim 31 wherein R is H and Y is H.
 33. The polymerof claim 32 wherein n/(n+m+p)% is from 25% to 95%.
 34. The polymer ofclaim 20 wherein X'--Q is --C₆ H₄ --CH₂ --Q and X is --C₆ H₄ --CH₂ --Cl.35. The polymer of claim 34 wherein R is H or methyl, Y is H or OH, andQ is --N⁺ R₁ R₂ R₃ Z⁻.
 36. The polymer of claim 21 wherein X'--Q is##STR23## wherein R is H and Z⁻ is halide.